Challenges and prospects of the role of solid electrolytes in the revitalization of lithium metal batteries

The scientific community is continuously committed to the search for new high energy electrochemical storage devices. In this regard, lithium metal batteries, due to their very high electrochemical energy storage capacity, appear to be a highly appealing choice. Unfortunately, the use of lithium metal as the anode may lead to some safety hazards due to its uneven deposition upon charging, resulting in dendrite growth and eventual shorting of the battery. This issue may be successfully addressed by using intrinsically safer electrolytes capable of establishing a physical barrier at the electrode interface. The most promising candidates are solid electrolytes, either polymeric or inorganic. The main purpose of this review is to describe the present status of worldwide research on these electrolyte materials together with a critical discussion of their transport properties and compatibility with metallic lithium, hoping to provide some general guidelines for the development of innovative and safe lithium metal batterie

Comparative study of the phase transition of Li1+xMn2-xO4 by anelastic spectroscopy and differential scanning calorimetry

Li1+xMn2xO4 is one of the most promising candidates as high performance cathode for lithium ion batteries. The stoichiometric compound is known to undergo a phase transition around room temperature, which has been widely studied and attributed either to Jahn–Teller effect or to charge ordering. For the applications it is important to suppress this phase transition, which lowers the electrochemical performances of the material. DSC measurements, which have been largely used in the literature to study the occurrence of the transformation, can detect a phase transition accompanied by latent heat only for x < 0.04. This fact has been generally accepted as a proof that the transformation is suppressed by doping. However, by using a technique extremely sensitive to rearrangements of atoms in the lattice, such as anelastic spectroscopy, we show that the phase transition persists up to x = 0.08, is shifted to lower temperatures, and changes its nature from first to higher order. The implications for the mechanism driving the transition and the similarities and differences with doped Fe3O4, which is the prototype of charge order transitions, are discussed

How much does size really matter? Exploring the limits of graphene as Li ion battery anode material

Abstract We unravel the role of flake dimensionality on the lithiation/de-lithiation processes and electrochemical performance of anodes based on few-(FLG) and multi-layer graphene (MLG) flakes prepared by liquid phase exfoliation (LPE) of pristine graphite. The flakes are sorted by lateral size (from 380 to 75 nm) and thickness from 20 (MLG) to 2 nm (FLG) exploiting a sedimentation-based separation in centrifugal field and, finally, deposited onto Cu disks for the realization of four binder-free anodes. The electrochemical results show that decreasing lateral size and thickness leads to an increase of the initial specific capacity from ≈590 to ≈1270mAhg −1 . However, an increasing irreversible capacity is also associated to the reduction of flakes' size. We find, in addition, that the preferential Li ions storage by adsorption rather than intercalation in small lateral size

Differentiation of haploid and diploid fertilities in Gracilaria chilensis affect ploidy ratio

Background Algal isomorphic biphasic life cycles alternate between free-living diploid (tetrasporophytes) and haploid (dioicious gametophytes) phases and the hypotheses explaining their maintenance are still debated. Classic models state that conditional differentiation between phases is required for the evolutionary stability of biphasic life cycles while other authors proposed that the uneven ploidy abundances observed in the field are explained by their cytological differences in spore production. Results We monitored the state and fate of individuals of the red seaweed Gracilaria chilensis periodically for 3 years in five intertidal pools from two sites with distinct conditions. We tested for differentiation in fecundity and spore survival among the gametophyte males and females (haploids) and the tetrasporophytes (diploids). We tested for the influence of fecundity and spore survival on the observed uneven ploidy abundances in recruits. The probability of a frond becoming fecund was size-dependent, highest for the haploid males and lowest for the haploid females, with the diploids displaying intermediate probabilities. Fecund diploids released more tetraspores than carpospores released by the haploid females. Spore survival depended on ploidy and on the local density of co-habiting adult fronds. An advantage of diploid over haploid germlings was observed at very low and very high adult fronds densities. Conclusions Neither spore production nor spore survival determined the highly variable ploidy ratio within G. chilensis recruits. This result invalidates the hypothesis of natural cytological differences in spore production as the only driver of uneven field ploidy abundances in this species. Diploid spores (carpospores) survived better than haploid spores (tetraspores), especially in locations and time periods that were associated with the occurrence of strong biotic and abiotic stressors. We hypothesise that carpospore survival is higher due to support by their haploid female progenitors passing-on nutrients and chemical compounds improving survival under stressful conditions.AHE was supported by fellowships SFRH/BPD/63703/2009, SFRH/BPD/ 107878/2015 and UID/Multi/04326/2016 of the National Science Foundation FCT of Portugal.info:eu-repo/semantics/publishedVersio

Anomalous Lattice Vibrations of Single and Few-Layer MoS2

Molybdenum disulfide (MoS2) of single and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S-Mo-S layers of the samples was independently determined by contact-mode atomic-force microscopy. Two Raman modes, E12g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be explained solely by van der Waals interlayer coupling, is attributed to Coulombic interactions and possible stacking-induced changes of the intralayer bonding. This work exemplifies the evolution of structural parameters in layered materials in changing from the 3-dimensional to the 2-dimensional regime.Comment: 14 pages, 4 figure

Variation in Community Structure across Vertical Intertidal Stress Gradients: How Does It Compare with Horizontal Variation at Different Scales?

In rocky intertidal habitats, the pronounced increase in environmental stress from low to high elevations greatly affects community structure, that is, the combined measure of species identity and their relative abundance. Recent studies have shown that ecological variation also occurs along the coastline at a variety of spatial scales. Little is known, however, on how vertical variation compares with horizontal variation measured at increasing spatial scales (in terms of sampling interval). Because broad-scale processes can generate geographical patterns in community structure, we tested the hypothesis that vertical ecological variation is higher than fine-scale horizontal variation but lower than broad-scale horizontal variation. To test this prediction, we compared the variation in community structure across intertidal elevations on rocky shores of Helgoland Island with independent estimates of horizontal variation measured at the scale of patches (quadrats separated by 10s of cm), sites (quadrats separated by a few m), and shores (quadrats separated by 100s to 1000s of m). The multivariate analyses done on community structure supported our prediction. Specifically, vertical variation was significantly higher than patch- and site-scale horizontal variation but lower than shore-scale horizontal variation. Similar patterns were found for the variation in abundance of foundation taxa such as Fucus spp. and Mastocarpus stellatus, suggesting that the effects of these canopy-forming algae, known to function as ecosystem engineers, may explain part of the observed variability in community structure. Our findings suggest that broad-scale processes affecting species performance increase ecological variability relative to the pervasive fine-scale patchiness already described for marine coasts and the well known variation caused by vertical stress gradients. Our results also indicate that experimental research aiming to understand community structure on marine shores should benefit from applying a multi-scale approach

Seafloor biodiversity of Canada's three oceans: patterns, hotspots and potential drivers

Aim We examined the relationships between bathymetry, latitude and energy and the diversity of marine benthic invertebrates across wide environmental ranges of Canada's three oceans. Location Canadian Pacific, Arctic and Atlantic Oceans from the intertidal zone to upper bathyal depths, encompassing 13 marine ecoregions. Methods We compiled 35 benthic datasets that encompass 3,337 taxa (70% identified to species and 21% to genus) from 13,172 samples spanning 6,117 sites. Partitioning the analyses by different gear types, ecoregions or sites, we used Hill numbers to examine spatial patterns in α‐diversity. We used resampling and extrapolation to standardized sampling effort and examined the effects of depth, latitude, chemical energy (export particulate organic carbon [POC] flux), thermal energy (bottom temperature) and seasonality of primary production on the benthic biodiversity. Results The Canadian Arctic harboured the highest benthic diversity (e.g. epifauna and common and dominant infauna species), whereas the lowest diversity was found in the Atlantic. The Puget Trough (Pacific), Beaufort Sea, Arctic Archipelago, Hudson Bay, Northern Labrador and Southern Grand Bank (Atlantic) were the “hotspots" of diversity among the ecoregions. The infauna and epifauna both exhibited hump‐shaped diversity–depth relationships, with peak diversity near shelf breaks; latitude (positively) predicted infaunal diversity, albeit weakly. Food supply, as inferred from primary production and depth, was more important than thermal energy in controlling diversity patterns. Limitations with respect to calculating POC flux in coastal (e.g. terrestrial runoff) and ice‐covered regions or biological interactions may explain the negative POC flux–infaunal diversity relationship. Main Conclusions We show previously unreported diversity hotspots in the Canadian Arctic and in other ecoregions. Our analyses reveal potential controlling mechanisms of large‐scale benthic biodiversity patterns in Canada's three oceans, which are inconsistent with the prevailing view of seafloor energy–diversity relationships. These results provide insightful information for conservation that can help to implement further MPA networks

The BenBioDen database, a global database for meio-, macro- and megabenthic biomass and densities

Benthic fauna refers to all fauna that live in or on the seafloor, which researchers typically divide into size classes meiobenthos (32/64 µm–0.5/1 mm), macrobenthos (250 µm–1 cm), and megabenthos (>1 cm). Benthic fauna play important roles in bioturbation activity, mineralization of organic matter, and in marine food webs. Evaluating their role in these ecosystem functions requires knowledge of their global distribution and biomass. We therefore established the BenBioDen database, the largest open-access database for marine benthic biomass and density data compiled so far. In total, it includes 11,792 georeferenced benthic biomass and 51,559 benthic density records from 384 and 600 studies, respectively. We selected all references following the procedure for systematic reviews and meta-analyses, and report biomass records as grams of wet mass, dry mass, or ash-free dry mass, or carbon per m2 and as abundance records as individuals per m2. This database provides a point of reference for future studies on the distribution and biomass of benthic fauna

In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.National Science Foundation (U.S.) (Materials Research Science and Engineering Center (MRSEC) Program, Award DMR-0819762)United States. Dept. of Energy (Assistant Secretary for Energy Efficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies of the U. S. Department of Energy under contract no. DE-AC03-76SF00098)Lawrence Berkeley National LaboratoryUnited States. Dept. of Energy (Office of Basic Energy Sciences, Materials Sciences and Engineering